JPH05186531A - Production of polyacetylenic conjugated polymer - Google Patents
Production of polyacetylenic conjugated polymerInfo
- Publication number
- JPH05186531A JPH05186531A JP4005226A JP522692A JPH05186531A JP H05186531 A JPH05186531 A JP H05186531A JP 4005226 A JP4005226 A JP 4005226A JP 522692 A JP522692 A JP 522692A JP H05186531 A JPH05186531 A JP H05186531A
- Authority
- JP
- Japan
- Prior art keywords
- group
- substrate
- film
- polyacetylene
- conjugated polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
- B05D1/185—Processes for applying liquids or other fluent materials performed by dipping applying monomolecular layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F38/00—Homopolymers and copolymers of compounds having one or more carbon-to-carbon triple bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ポリアセチレン型（超
長）共役ポリマーの製造方法に関する。更に詳しくは、
導電性や非線形光学効果を示し電気材料等に有用なポリ
アセチレン結合を有する有機物質に関するものである。TECHNICAL FIELD The present invention relates to a method for producing a polyacetylene type (ultra-long) conjugated polymer. For more details,
The present invention relates to an organic substance having a polyacetylene bond which exhibits conductivity and a nonlinear optical effect and is useful as an electric material and the like.
【０００２】[0002]
【従来の技術】アセチレン誘導体のポリマ−は、パイ電
子共役系を持つ一次元の主鎖を分子内に保有しているこ
とで、導電性や非線形光学効果を持つことから光、電子
機能材料として広く研究されている。2. Description of the Related Art Polymers of acetylene derivatives have conductivity and nonlinear optical effects because they have a one-dimensional main chain having a pi-electron conjugated system in the molecule. Has been widely studied.
【０００３】また、ポリアセチレンの製造方法として
は、白川らが用いたアセチレンガスをチグラー・ナッタ
触媒で重合する方法がよく知られている（シンセティッ
ク メタルス、１巻、１７５頁(1979/1980) （スイ
ス）。As a method for producing polyacetylene, a method of polymerizing acetylene gas used by Shirakawa et al. With a Ziegler-Natta catalyst is well known (Synthetic Metals, Vol. 1, pp. 175 (1979/1980) (Switzerland). ).
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、現在知
られているポリアセチレン誘導体は、酸素を含む雰囲気
中では、熱や圧力あるいは紫外線などに対して不安定で
ある。However, currently known polyacetylene derivatives are unstable to heat, pressure or ultraviolet rays in an atmosphere containing oxygen.
【０００５】そこで、安定化させる研究が進められてい
るが、未だにアセチレン誘導体ポリマを安定化する方法
は見いだされていない。本発明は、従来の欠点に鑑みな
されたもので、酸素を含む雰囲気中で安定なポリアセチ
レン型超長共役ポリマ−の製造方法を提供することを目
的とする。Therefore, researches for stabilizing the acetylene derivative polymers have been made, but no method for stabilizing the acetylene derivative polymer has been found. The present invention has been made in view of the conventional drawbacks, and an object of the present invention is to provide a method for producing a polyacetylene type ultralong conjugated polymer which is stable in an atmosphere containing oxygen.
【０００６】[0006]
【課題を解決するための手段】前記目的を達成するた
め、本発明のポリアセチレン型共役ポリマーの製造方法
の第１番目の発明は、アセチレン基と−Ｓｉ−Ｃｌ基を
含む化学吸着物質を溶解させた非水系の第１の有機溶媒
中に、表面が前記化学吸着物質と活性な基を有する基板
を浸漬し、前記基板表面に化学吸着膜を形成し、次いで
チ−グラ・ナッタ触媒を含む第２の有機溶媒中に前記化
学吸着膜が形成された基板を浸漬し、前記化学吸着膜の
アセチレン基の部分を重合させる工程を含むという構成
を備えたものである。In order to achieve the above object, the first invention of the method for producing a polyacetylene type conjugated polymer of the present invention is to dissolve a chemical adsorbent containing an acetylene group and a -Si-Cl group. A substrate having a surface having the chemisorbing substance and an active group is immersed in a non-aqueous first organic solvent to form a chemisorbing film on the substrate surface, and then a substrate containing a Ziegler-Natta catalyst is formed. It is provided with a constitution including a step of immersing the substrate on which the chemical adsorption film is formed in the second organic solvent and polymerizing a portion of the acetylene group of the chemical adsorption film.
【０００７】次に第２番目の発明は、ジアセチレン基と
−Ｓｉ−Ｃｌ基を含む化学吸着物質を溶解させた非水系
の第１の有機溶媒中に、表面が前記化学吸着物質と活性
な基を有する基板を浸漬し、前記基板表面に化学吸着膜
を形成し、次いでチ−グラ・ナッタ触媒を含む第２の有
機溶媒中に前記化学吸着膜が形成された基板を浸漬し、
前記化学吸着膜のジアセチレン基の部分を重合させる工
程を含むという構成を備えたものである。A second aspect of the present invention is that the surface of the non-aqueous first organic solvent in which the chemical adsorbing substance containing a diacetylene group and a --Si--Cl group is dissolved is active. Immersing the substrate having a group to form a chemisorption film on the substrate surface, and then dipping the substrate having the chemisorption film formed in a second organic solvent containing a Ziegler-Natta catalyst;
The chemical adsorption film has a configuration including a step of polymerizing a diacetylene group portion.
【０００８】[0008]
【作用】前記本発明の第１発明及び第２発明の構成によ
れば、一端に−Ｓｉ−Ｃｌ基を持つ直鎖上の炭化水素誘
導体を用いると、有機溶媒中で化学吸着により基板表面
に化学吸着膜を高密度（最密充填）で形成できる。さら
に前記化学吸着膜表面を酸素を含むガス中で高エネルギ
ー線照射して表面を親水性化することにより単分子膜の
累積膜を形成することができる。従って、直鎖状炭化水
素の一部にアセチレン基を含む物質を用い化学吸着法を
行えば、数十オングストローム（数ナノメーター）オー
ダのアセチレン誘導体の化学吸着膜を高密度で形成で
き、さらに多層の累積膜も容易に得ることができる。According to the first and second aspects of the present invention, when a linear hydrocarbon derivative having a --Si--Cl group at one end is used, it is chemically adsorbed on the substrate surface in an organic solvent. The chemisorption film can be formed with high density (closest packing). Further, by irradiating the surface of the chemical adsorption film with a high energy beam in a gas containing oxygen to make the surface hydrophilic, a cumulative film of a monomolecular film can be formed. Therefore, if a chemical adsorption method is performed using a substance containing an acetylene group as a part of a straight-chain hydrocarbon, a chemical adsorption film of an acetylene derivative on the order of several tens of angstroms (several nanometers) can be formed with high density, A cumulative film of can be easily obtained.
【０００９】この方法により累積された単分子膜を、チ
−グラナッタ触媒を含む有機溶媒中に浸漬し、前記単分
子膜のアセチレン基の部分を重合させると、超高分子量
で共役系が非常に長いポリアセチレンが高密度で形成で
きる。そのため、酸素の攻撃を受けにくくなり、酸素を
含む雰囲気中でも安定なポリアセチレンが形成される。
つまり、高密度でかつ一定の配向性を保った状態でチ−
グラ触媒を用いてアセチレン誘導体の分子を重合するこ
とにより、共役系が連続した直鎖状で超高分子量の酸素
を含む雰囲気中で、熱や圧力あるいは紫外線などにたい
して安定なポリマー（超長共役ポリマー）をつくれる。When the monomolecular film accumulated by this method is immersed in an organic solvent containing a Thi-Granatta catalyst to polymerize a portion of the acetylene group of the monomolecular film, a conjugated system having an ultrahigh molecular weight is formed. Long polyacetylene can be formed with high density. Therefore, it is less likely to be attacked by oxygen, and stable polyacetylene is formed even in an atmosphere containing oxygen.
In other words, it is possible to achieve high density and maintain a constant orientation.
By polymerizing acetylene derivative molecules using a Gura catalyst, a polymer that is stable to heat, pressure, ultraviolet rays, etc. in an atmosphere containing linear and ultra-high molecular weight oxygen with a continuous conjugated system (ultra-long conjugated polymer) ) Can be made.
【００１０】次に化学吸着膜が単分子膜であるという本
発明の好ましい構成によれば、前記ナノメーターレベル
の極薄の化学吸着膜を均一に形成することができる。ま
た、アセチレン基またはジアセチレン基に−Ｓｉ（ＣＨ
3 ）3 が結合しているという本発明の好ましい構成によ
れば、分子末端の安定化をはかり、かつ化学吸着膜を形
成した後、アルカリ水溶液で処理することにより−Ｓｉ
（ＣＨ3 ）3 基を脱離することができる。これにより、
アセチレン基またはジアセチレン基を化学吸着膜の最外
表面に配置させることができる。Next, according to the preferable constitution of the present invention in which the chemical adsorption film is a monomolecular film, the ultra-thin chemical adsorption film at the nanometer level can be uniformly formed. In addition, the acetylene group or the diacetylene group has -Si (CH
3 ) According to a preferred structure of the present invention in which 3 is bonded, the molecular end is stabilized, and after forming a chemisorption film, it is treated with an alkaline aqueous solution to obtain -Si.
The (CH 3 ) 3 group can be eliminated. This allows
An acetylene group or a diacetylene group can be arranged on the outermost surface of the chemisorption film.
【００１１】さらにチ−グラ・ナッタ触媒が、周期律表
の第４族ないし第８族の遷移金属の化合物を周期律表第
１族ないし第３族ａの元素の有機金属化合物で処理して
調製されたものであるとという本発明の構成によれば、
触媒活性の高いものとすることができる。Further, a Ziegler-Natta catalyst treats a compound of a transition metal of Groups 4 to 8 of the periodic table with an organometallic compound of an element of Group 1 to 3 of the periodic table. According to the constitution of the present invention that is prepared,
It can have a high catalytic activity.
【００１２】[0012]
【実施例】以下、実施例を用いて本発明の詳細を説明す
る。なお、本発明は下記の実施例に限定されることはな
い。EXAMPLES The present invention will be described in detail below with reference to examples. The present invention is not limited to the examples below.
【００１３】本発明の一実施例を図１に示す。一方の分
子末端にアセチレン基と他方の分子末端にトリクロロシ
リル基を含む化学吸着材を溶解させた非水系の有機溶媒
中に、親水性の基板として−ＯＨ基を有し、ＳｉＯ2 の
形成されたＳｉ基板１を浸漬し、−ＳｉＣｌ基と基板表
面の前記−ＯＨ基が反応して脱塩酸する。次いで非水溶
液で洗浄して未反応物を除去すると、基板表面に下記式
（化１）で示す単分子膜２が形成される（図１）。An embodiment of the present invention is shown in FIG. In a non-aqueous organic solvent in which a chemical adsorbent containing an acetylene group at one molecular end and a trichlorosilyl group at the other molecular end is dissolved, it has a —OH group as a hydrophilic substrate and forms SiO 2. Then, the Si substrate 1 is immersed, and the --SiCl group reacts with the --OH group on the substrate surface to dehydrochlorine. Then, by washing with a non-aqueous solution to remove unreacted materials, a monomolecular film 2 represented by the following formula (Formula 1) is formed on the substrate surface (FIG. 1).
【００１４】[0014]
【化１】 [Chemical 1]
【００１５】ここで、基板表面に前記式（化１）で示す
単分子膜２が形成できていることは、ＦＴＩＲにて確認
した。また、前記の方法で累積された吸着膜はアルコ−
ル溶媒には不溶性であることが確認できた。Here, it was confirmed by FTIR that the monomolecular film 2 represented by the above formula (Formula 1) was formed on the surface of the substrate. In addition, the adsorbed film accumulated by the above method is
It was confirmed that the solvent was insoluble in the solvent.
【００１６】次に、チ−グラ・ナッタ触媒を含む有機溶
媒に、前記単分子膜が一層形成された基板を浸漬する
と、重合反応が起こり、図２に示すポリアセチレン３が
生成する。ポリアセチレンが製造されたことはＦＴＩＲ
スペクトルで明かとなった。Next, when the substrate on which the monomolecular film is formed is immersed in an organic solvent containing a Ziegler-Natta catalyst, a polymerization reaction occurs and polyacetylene 3 shown in FIG. 2 is produced. The fact that polyacetylene was produced is FTIR
It's revealed in the spectrum.
【００１７】次に図３は、末端にジアセチレン基とトリ
クロロシリル基を含む化合物を用いたポリアセチレンの
製造方法を示す図である。末端にジアセチレン基とトリ
クロロシリル基を含む化合物を溶解させた非水系の有機
溶媒中に、親水性の基板としてＳｉＯ2 の形成されたＳ
ｉ基板１を浸漬すると、−ＳｉＣｌ基と基板表面のＳｉ
Ｏ2 とともに形成されている−ＯＨ基が反応して脱塩酸
する。次いで非水溶液で洗浄して未反応物を除去する
と、基板表面に下記式（化２）で示す単分子膜４が形成
される（図４）。Next, FIG. 3 is a diagram showing a method for producing polyacetylene using a compound having a diacetylene group and a trichlorosilyl group at the terminal. In a non-aqueous organic solvent in which a compound containing a diacetylene group and a trichlorosilyl group is dissolved at the terminal, SiO 2 as a hydrophilic substrate on which S 2 is formed is formed.
When the i substrate 1 is dipped, -SiCl groups and Si on the substrate surface
-OH group with O 2 are formed to dehydrochlorination react. Then, by washing with a non-aqueous solution to remove unreacted substances, a monomolecular film 4 represented by the following formula (Formula 2) is formed on the substrate surface (FIG. 4).
【００１８】[0018]
【化２】 [Chemical 2]
【００１９】ここで、基板表面に前記式（化２）で示す
単分子膜４が形成できていることは、ＦＴＩＲにて確認
できた。なお、上述の方法で累積された吸着膜はアルコ
−ル溶媒には不溶性であることも確認できた。It was confirmed by FTIR that the monomolecular film 4 represented by the above formula (Formula 2) was formed on the surface of the substrate. It was also confirmed that the adsorbed film accumulated by the above method was insoluble in the alcohol solvent.
【００２０】次に、チ−グラ・ナッタ触媒を含む有機溶
媒に、前記単分子膜が一層形成された基板を浸漬する
と、重合反応が起こり、図４に示すポリアセチレン５が
生成する。ポリアセチレンが製造されたことはＦＴＩＲ
スペクトルで明かとなった。Next, when the substrate having the monomolecular film formed thereon is immersed in an organic solvent containing a Ziegler-Natta catalyst, a polymerization reaction occurs and polyacetylene 5 shown in FIG. 4 is produced. The fact that polyacetylene was produced is FTIR
It's revealed in the spectrum.
【００２１】本発明に使用しうるアセチレン基と−Ｓｉ
−Ｃｌ基を含む物質として、下記式（化３）の化合物を
一例としてあげることができる。Acetylene group and --Si which can be used in the present invention
As the substance containing a —Cl group, a compound represented by the following formula (Formula 3) can be given as an example.
【００２２】[0022]
【化３】 [Chemical 3]
【００２３】本発明に使用しうるジアセチレン基と−Ｓ
ｉ−Ｃｌ基を含む物質として、下記式（化４）の化合物
を一例としてあげることができる。The diacetylene group and --S that can be used in the present invention.
As the substance containing an i-Cl group, a compound represented by the following formula (Formula 4) can be given as an example.
【００２４】[0024]
【化４】 [Chemical 4]
【００２５】また、分子末端の安定化をはかるためにア
セチレン基に−ＳｉＭｅ3 基のついた物質を用いること
ができる。下記式（化５）の化合物を一例としてあげる
ことができる。Further, in order to stabilize the molecular ends, a substance having an acetylene group with a —SiMe 3 group can be used. A compound represented by the following formula (Formula 5) can be given as an example.
【００２６】[0026]
【化５】 [Chemical 5]
【００２７】この場合は、吸着後１０％ＫＯＨ水溶液に
浸漬すると−Ｓｉ（ＣＨ3 ）3 基が脱離されて同様に、
下記式（化６）及び（化７）の単分子膜が形成できる。In this case, when it is immersed in a 10% KOH aqueous solution after adsorption, the --Si (CH 3 ) 3 group is desorbed, and similarly,
A monomolecular film represented by the following formulas (Formula 6) and (Formula 7) can be formed.
【００２８】[0028]
【化６】 [Chemical 6]
【００２９】[0029]
【化７】 [Chemical 7]
【００３０】本発明に用いることのできるチ−グラ・ナ
ッタ触媒は、周期律表の第４族ないし第８族の遷移金属
の化合物を周期律表第１族ないし第３族ａの元素の有機
金属化合物と反応させて得ることができる。The Ziegler-Natta catalyst that can be used in the present invention is a compound of a transition metal of Groups 4 to 8 of the Periodic Table, an organic compound of an element of Group 1 to 3 of the Periodic Table. It can be obtained by reacting with a metal compound.
【００３１】このような有機金属化合物としては例えば
アルキルアルミニウム化合物、亜鉛アルキル化合物また
はリチウムアルキル化合物が利用でき、第４族ないし第
８族の遷移金属の化合物としてはアルコキサイドまたは
ハロゲン化物が使用できる。一例として下記式（化８）
のものがあげられる。As such an organometallic compound, for example, an alkylaluminum compound, a zinc alkyl compound or a lithium alkyl compound can be used, and as a compound of a transition metal of Group 4 to Group 8 an alkoxide or a halide can be used. As an example, the following formula (Formula 8)
I can give you one.
【００３２】[0032]
【化８】 [Chemical 8]
【００３３】次に、具体的実施例を用いて本発明を説明
する。 実施例１ 直径３インチの酸化膜（ＳｉＯ2 ）を形成したＳｉ基板
を、下記式（化９）に示す反応化学吸着物質ω−ノナデ
シルイノイックトリクロロシラン（ＮＣＳ）の１０-2mo
l ／ｌ溶液（80wt% ヘキサデカン＋12wt% 四塩化炭素＋
８wt% クロロホルム）に室温、窒素雰囲気下で１時間浸
漬した。Next, the present invention will be described with reference to specific examples. Example 1 An Si substrate on which an oxide film (SiO 2 ) having a diameter of 3 inches was formed was treated with 10 −2 mo of a reaction chemisorption substance ω-nonadecylinoic trichlorosilane (NCS) represented by the following formula (Formula 9).
l / l solution (80wt% hexadecane + 12wt% carbon tetrachloride +
It was immersed in 8 wt% chloroform) at room temperature under a nitrogen atmosphere for 1 hour.
【００３４】[0034]
【化９】 [Chemical 9]
【００３５】次いで前記基板を取り出し、クロロホルム
で洗浄して未反応化学吸着物質を除去し、しかる後純水
で洗浄し、単分子膜をＳｉ表面に形成した。次に、前記
単分子膜を形成したＳｉ基板をトリエチルアルミニウム
の５×１０-2mol ／ｌ溶液（トルエン）とテトラブチル
チタネートの２．５×１０-2mol ／ｌ溶液（トルエン）
からなる混合触媒に浸漬して重合した。２時間後、トル
エンで洗浄し、試料を得た。Next, the substrate was taken out and washed with chloroform to remove unreacted chemisorbed substances, and then washed with pure water to form a monomolecular film on the Si surface. Next, the Si substrate having the monomolecular film formed thereon was treated with a 5 × 10 −2 mol / l solution of triethylaluminum (toluene) and a 2.5 × 10 −2 mol / l solution of tetrabutyl titanate (toluene).
Polymerization was carried out by immersing in a mixed catalyst consisting of. After 2 hours, it was washed with toluene to obtain a sample.
【００３６】実施例２ 実施例１のω−ノナデシルイノイックトリクロロシラン
を、下記式（化１０）に示す反応化学吸着物質１−（ト
リメチルシリル）−ω−ノナデシルイノイックトリクロ
ロシラン（ＴＭＳ−ＮＣＳ）に変えて同様の実験をし
た。Example 2 The ω-nonadecylinoic trichlorosilane of Example 1 was converted into a chemically adsorbed substance 1- (trimethylsilyl) -ω-nonadecylinoic trichlorosilane (TMS-NCS) represented by the following formula (Formula 10). ) Was changed to the same experiment.
【００３７】[0037]
【化１０】 [Chemical 10]
【００３８】実施例３ 実施例１のω−ノナデシルイノイックトリクロロシラン
を下記式（化１１）に示す反応化学吸着物質に変えて同
様の実験をした。Example 3 A similar experiment was conducted by changing the ω-nonadecylinoic trichlorosilane of Example 1 to a reaction chemisorption material represented by the following formula (Formula 11).
【００３９】[0039]
【化１１】 [Chemical 11]
【００４０】実施例４ 実施例１のω−ノナデシルイノイックトリクロロシラン
を下記式（化１２）に示す反応化学吸着物質に変えて同
様の実験をした。Example 4 A similar experiment was conducted by changing the ω-nonadecylinoic trichlorosilane of Example 1 to a reaction chemisorption substance represented by the following formula (Formula 12).
【００４１】[0041]
【化１２】 [Chemical 12]
【００４２】実施例５ 実施例１のω−ノナデシルイノイックトリクロロシラン
を下記式（化１３）に示す反応化学吸着物質に変えて同
様の実験をした。Example 5 A similar experiment was conducted by changing the ω-nonadecylinoic trichlorosilane of Example 1 to a reaction chemisorption material represented by the following formula (Formula 13).
【００４３】[0043]
【化１３】 [Chemical 13]
【００４４】実施例６ 実施例１のω−ノナデシルイノイックトリクロロシラン
を下記式（化１４）に示す反応化学吸着物質に変えて同
様の実験をした。Example 6 A similar experiment was conducted by changing the ω-nonadecylinoic trichlorosilane of Example 1 to a reaction chemisorption substance represented by the following formula (Formula 14).
【００４５】[0045]
【化１４】 [Chemical 14]
【００４６】実施例７ 実施例１の混合触媒をトリオクチルアルミニウムの５×
１０-2mol ／ｌ溶液（トルエン）とテトラブチルチタネ
ートの２．５×１０-2mol ／ｌ溶液（トルエン）からな
る混合触媒に変えて同様の実験をした。Example 7 The mixed catalyst of Example 1 was mixed with 5 × of trioctylaluminum.
The same experiment was conducted by changing to a mixed catalyst composed of a 10 -2 mol / l solution (toluene) and a 2.5 x 10 -2 mol / l solution of tetrabutyl titanate (toluene).
【００４７】実施例８ 実施例１の混合触媒をトリエチルアルミニウムの５×１
０-2mol ／ｌ溶液（トルエン）とテトラクロロチタンの
２．５×１０-2mol ／ｌ溶液（トルエン）からなる混合
触媒に変えて同様の実験をした。Example 8 The mixed catalyst of Example 1 was mixed with 5 × 1 of triethylaluminum.
The same experiment was performed by changing to a mixed catalyst composed of a 0 -2 mol / l solution (toluene) and a tetrachlorotitanium 2.5 x 10 -2 mol / l solution (toluene).
【００４８】実施例９ 実施例１の混合触媒をトリエチルアルミニウムの５×１
０-2mol ／ｌ溶液（トルエン）とテトラクロロバナジウ
ムの２．５×１０-2mol ／ｌ溶液（トルエン）からなる
混合触媒に変えて同様の実験をした。Example 9 The mixed catalyst of Example 1 was mixed with 5 × 1 of triethylaluminum.
The same experiment was conducted by changing to a mixed catalyst composed of a 0 -2 mol / l solution (toluene) and a 2.5 x 10 -2 mol / l solution of tetrachlorovanadium (toluene).
【００４９】実施例１０ 実施例１の混合触媒をジエチル亜鉛の５×１０-2mol ／
ｌ溶液（トルエン）とテトラブチルチタネートの２．５
×１０-2mol ／ｌ溶液（トルエン）からなる混合触媒に
変えて同様の実験をした。Example 10 The mixed catalyst of Example 1 was mixed with diethyl zinc at 5 × 10 -2 mol / mol.
1 solution (toluene) and tetrabutyl titanate 2.5
The same experiment was conducted by changing to a mixed catalyst consisting of a solution of 10-2 mol / l (toluene).
【００５０】実施例１１ 実施例１の混合触媒をブチルリチウムの５×１０-2mol
／ｌ溶液（トルエン）とテトラブチルチタネートの２．
５×１０-2mol ／ｌ溶液（トルエン）からなる混合触媒
に変えて同様の実験をした。Example 11 The mixed catalyst of Example 1 was mixed with 5 × 10 -2 mol of butyllithium.
/ L solution (toluene) and tetrabutyl titanate 2.
The same experiment was conducted by changing to a mixed catalyst composed of a 5 × 10 -2 mol / l solution (toluene).
【００５１】比較例１ トリエチルアルミニウムの５×１０-2mol ／ｌ溶液（ト
ルエン）とテトラブチルチタネートの２．５×１０-2mo
l ／ｌ溶液（トルエン）からなる混合触媒を用いて、ア
セチレンガスを重合して、ポリアセチレンフィルムを得
た。Comparative Example 1 Triethylaluminum 5 × 10 -2 mol / l solution (toluene) and tetrabutyl titanate 2.5 × 10 -2 mo
Acetylene gas was polymerized using a mixed catalyst composed of l / l solution (toluene) to obtain a polyacetylene film.
【００５２】実施例１〜１１および比較例１の試料を６
０℃の温度雰囲気でに３０日間放置し、放置前後のＦＴ
ＩＲを比較した。比較例の試料では、３４５０ｃｍ-1に
吸収ピークが現れ、酸化が進行していたが、本発明の実
施例の試料ではＦＴＩＴに変化はなく酸化は起こってい
なかった。Six samples of Examples 1 to 11 and Comparative Example 1 were prepared.
FT before and after leaving for 30 days in 0 ° C temperature atmosphere
IR was compared. In the sample of the comparative example, an absorption peak appeared at 3450 cm −1 and oxidation proceeded, but in the sample of the example of the present invention, FTIT did not change and oxidation did not occur.
【００５３】また、前述の実施例では１層化学吸着膜を
形成し重合を行う方法について述べたが吸着膜を多層積
層した後で重合反応を行っても良いし、あるいは吸着膜
の形成−重合反応を交互に行ってもポリアセチレンの多
層分子膜の作製が可能なことは明らかであろう。Further, in the above-mentioned embodiment, the method of forming a one-layered chemisorption film and polymerizing is described, but the polymerization reaction may be carried out after the adsorption films are laminated in multiple layers, or the adsorption film formation-polymerization It will be apparent that the polyacetylene multilayer molecular film can be prepared even by performing the reactions alternately.
【００５４】以上説明した通り、本発明の実施例によれ
ば、理論的には共役系が連続して数ｍｍ或は数ｃｍ以上
の長さを持つ直鎖状の超高分子量のポリアセチレンの製
造も可能であるため、非線形光学効果を利用したデバイ
スの製作には極めて有効である。また、今後さらに原料
となるアセチレンやジアセチレン誘導体モノマーの種類
や製造条件を適正化することにより、共役系が連続して
数十ｃｍ或は数ｍ以上の長さを持つ直鎖状で超高分子量
の安定なポリアセチレンの製造も可能になると思われ
る。これにより、この方法で冷却を必要としない有機超
電導物質を製造し得る。As described above, according to the embodiment of the present invention, theoretically, a linear ultrahigh molecular weight polyacetylene having a conjugated system having a length of several mm or several cm or more is produced. Since it is also possible, it is extremely effective for manufacturing a device utilizing the nonlinear optical effect. In addition, by optimizing the types of acetylene and diacetylene derivative monomers, which are the raw materials, and manufacturing conditions, the conjugated system will continue to be linear and ultra-high with a length of several tens of centimeters or several meters or more. It would also be possible to produce polyacetylene having a stable molecular weight. Thereby, an organic superconducting material which does not require cooling can be produced by this method.
【００５５】[0055]
【発明の効果】以上説明した通り、本発明の方法を用い
ることにより、酸素を含む雰囲気中で安定で、導電性や
非線形光学効果の優れたポリアセチレンのポリマーを高
能率に製造できる。また、高密度でかつ一定の配向性を
保った状態でチ−グラ触媒を用いてアセチレン誘導体の
分子を重合することにより、共役系が連続した直鎖状で
超高分子量の酸素を含む雰囲気中で、熱や圧力あるいは
紫外線などにたいして安定なポリマー（超長共役ポリマ
ー）を形成できる。As described above, by using the method of the present invention, a polyacetylene polymer which is stable in an atmosphere containing oxygen and has excellent conductivity and nonlinear optical effect can be produced with high efficiency. Further, by polymerizing the molecules of the acetylene derivative using a Ziegler catalyst in a state of maintaining a high density and a constant orientation, in an atmosphere containing a linear and ultra-high molecular weight oxygen in which the conjugated system is continuous. Thus, it is possible to form a stable polymer (ultra long conjugated polymer) against heat, pressure or ultraviolet rays.
【図１】本発明の一実施例を示すアセチレン系吸着膜を
１層形成した基板の分子オーダーの拡大断面概念図であ
る。FIG. 1 is an enlarged cross-sectional conceptual diagram of a molecular order of a substrate on which one layer of an acetylene-based adsorption film according to an embodiment of the present invention is formed.
【図２】本発明の一実施例を示すアセチレン系吸着膜を
重合したポリアセチレン吸着膜の形成された基板の分子
オーダーの拡大断面概念図である。FIG. 2 is an enlarged cross-sectional conceptual view of a molecular order of a substrate on which a polyacetylene adsorption film obtained by polymerizing an acetylene adsorption film according to an embodiment of the present invention is formed.
【図３】本発明の別の実施例を示すジアセチレン系吸着
膜を１層形成した基板の分子オーダーの拡大断面概念図
である。FIG. 3 is an enlarged cross-sectional conceptual diagram of a molecular order of a substrate on which one layer of a diacetylene-based adsorption film according to another embodiment of the present invention is formed.
【図４】本発明の別の実施例を示すジアセチレン系吸着
膜を重合したポリアセチレン吸着膜の形成された基板の
分子オーダーの拡大断面概念図である。FIG. 4 is an enlarged cross-sectional conceptual view of a molecular order of a substrate on which a polyacetylene adsorption film obtained by polymerizing a diacetylene-based adsorption film according to another embodiment of the present invention is formed.
１ ＳｉＯ2 ／Ｓｉ基板 ２ アセチレン系単分子吸着膜 ３ アセチレンを重合したポリアセチレン単分子吸着膜 ４ ジアセチレン系単分子吸着膜 ５ ジアセチレンを重合したポリアセチレン単分子吸着
膜1 SiO 2 / Si substrate 2 Acetylene-based monomolecular adsorption film 3 Acetylene-polymerized polyacetylene monomolecular adsorption film 4 Diacetylene-based monomolecular adsorption film 5 Diacetylene-polymerized polyacetylene monomolecular adsorption film
Claims (5)
学吸着物質を溶解させた非水系の第１の有機溶媒中に、
表面が前記化学吸着物質と活性な基を有する基板を浸漬
し、前記基板表面に化学吸着膜を形成し、次いでチ−グ
ラ・ナッタ触媒を含む第２の有機溶媒中に前記化学吸着
膜が形成された基板を浸漬し、前記化学吸着膜のアセチ
レン基の部分を重合させる工程を含むポリアセチレン型
共役ポリマーの製造方法。1. A non-aqueous first organic solvent in which a chemisorption substance containing an acetylene group and a —Si—Cl group is dissolved,
A substrate having a surface having the chemisorbing substance and an active group is dipped to form a chemisorption film on the substrate surface, and then the chemisorption film is formed in a second organic solvent containing a Ziegler-Natta catalyst. A method for producing a polyacetylene-type conjugated polymer, which comprises a step of immersing the prepared substrate and polymerizing a portion of the acetylene group of the chemical adsorption film.
化学吸着物質を溶解させた非水系の第１の有機溶媒中
に、表面が前記化学吸着物質と活性な基を有する基板を
浸漬し、前記基板表面に化学吸着膜を形成し、次いでチ
−グラ・ナッタ触媒を含む第２の有機溶媒中に前記化学
吸着膜が形成された基板を浸漬し、前記化学吸着膜のジ
アセチレン基の部分を重合させる工程を含むポリアセチ
レン型共役ポリマーの製造方法。2. A substrate having a surface having the chemical adsorbent and an active group is immersed in a non-aqueous first organic solvent in which a chemical adsorbent containing a diacetylene group and a —Si—Cl group is dissolved. A chemisorptive film is formed on the surface of the substrate, and the chemisorptive film-formed substrate is immersed in a second organic solvent containing a Ziegler-Natta catalyst to remove the diacetylene group of the chemisorptive film. A method for producing a polyacetylene-type conjugated polymer, which comprises a step of polymerizing a portion.
たは２に記載のポリアセチレン型共役ポリマーの製造方
法。3. The method for producing a polyacetylene-type conjugated polymer according to claim 1, wherein the chemisorption film is a monomolecular film.
Ｓｉ（ＣＨ3 ）3 が結合している請求項１または２に記
載のポリアセチレン型共役ポリマーの製造方法。4. An acetylene group or a diacetylene group-
The method for producing a polyacetylene-type conjugated polymer according to claim 1, wherein Si (CH 3 ) 3 is bonded.
４族ないし第８族の遷移金属の化合物を周期律表第１族
ないし第３族ａの元素の有機金属化合物で処理して調製
されたものである請求項１または２に記載のポリアセチ
レン型共役ポリマーの製造方法。5. A Ziegler-Natta catalyst treats a compound of a transition metal of Groups 4 to 8 of the Periodic Table with an organometallic compound of an element of Group 1 to 3 of the Periodic Table. The method for producing a polyacetylene-type conjugated polymer according to claim 1 or 2, which is prepared by
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4005226A JPH08846B2 (en) | 1992-01-14 | 1992-01-14 | Method for producing polyacetylene type conjugated polymer |
| US07/993,022 US5270417A (en) | 1992-01-14 | 1992-12-18 | Method of manufacturing a polyacetylene conjugate polymer |
| DE69322176T DE69322176T2 (en) | 1992-01-14 | 1993-01-11 | Process for the preparation of a conjugated acetylene polymer |
| EP93100300A EP0552637B1 (en) | 1992-01-14 | 1993-01-11 | Method of manufacturing a polyacetylene conjugate polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4005226A JPH08846B2 (en) | 1992-01-14 | 1992-01-14 | Method for producing polyacetylene type conjugated polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05186531A true JPH05186531A (en) | 1993-07-27 |
| JPH08846B2 JPH08846B2 (en) | 1996-01-10 |
Family
ID=11605277
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4005226A Expired - Fee Related JPH08846B2 (en) | 1992-01-14 | 1992-01-14 | Method for producing polyacetylene type conjugated polymer |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5270417A (en) |
| EP (1) | EP0552637B1 (en) |
| JP (1) | JPH08846B2 (en) |
| DE (1) | DE69322176T2 (en) |
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| JPS56115305A (en) * | 1980-02-18 | 1981-09-10 | Showa Denko Kk | Preparation of swollen acetylene high polymer membrane |
| JPS6239606A (en) * | 1985-08-15 | 1987-02-20 | Agency Of Ind Science & Technol | Production of polyphenylethynylacetylene and phenyl derivative thereof |
| JPH01275614A (en) * | 1988-04-28 | 1989-11-06 | Matsushita Electric Ind Co Ltd | Production of extraordinarily long polyacetylene or polyacene conjugated polymer |
| JPH03229710A (en) * | 1990-02-05 | 1991-10-11 | Matsushita Electric Ind Co Ltd | Production of highly orienting conjugated polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2555590B1 (en) * | 1983-11-29 | 1986-06-20 | Elf Aquitaine | PROCESS FOR THE MANUFACTURE OF POLYACETYLENE |
| EP0339677B1 (en) * | 1988-04-28 | 1992-11-11 | Matsushita Electric Industrial Co., Ltd. | Process for producing polyacetylene or polyacene type super long conjugated polymers |
| US5057339A (en) * | 1988-12-29 | 1991-10-15 | Matsushita Electric Industrial Co., Ltd. | Metallized polyacetylene-type or polyacene-type ultralong conjugated polymers and process for producing the same |
| EP0385656B1 (en) * | 1989-02-27 | 1995-05-10 | Matsushita Electric Industrial Co., Ltd. | A process for the production of a highly-orientated ultralong conjugated polymer |
-
1992
- 1992-01-14 JP JP4005226A patent/JPH08846B2/en not_active Expired - Fee Related
- 1992-12-18 US US07/993,022 patent/US5270417A/en not_active Expired - Lifetime
-
1993
- 1993-01-11 DE DE69322176T patent/DE69322176T2/en not_active Expired - Fee Related
- 1993-01-11 EP EP93100300A patent/EP0552637B1/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56115305A (en) * | 1980-02-18 | 1981-09-10 | Showa Denko Kk | Preparation of swollen acetylene high polymer membrane |
| JPS6239606A (en) * | 1985-08-15 | 1987-02-20 | Agency Of Ind Science & Technol | Production of polyphenylethynylacetylene and phenyl derivative thereof |
| JPH01275614A (en) * | 1988-04-28 | 1989-11-06 | Matsushita Electric Ind Co Ltd | Production of extraordinarily long polyacetylene or polyacene conjugated polymer |
| JPH03229710A (en) * | 1990-02-05 | 1991-10-11 | Matsushita Electric Ind Co Ltd | Production of highly orienting conjugated polymer |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999006415A1 (en) * | 1997-07-31 | 1999-02-11 | Matsushita Electric Industrial Co., Ltd. | Chemisorptive substance, aligned liquid-crystal film and liquid-crystal display element both made by using the same, and processes for producing these |
| US6495221B1 (en) | 1997-07-31 | 2002-12-17 | Matsushita Electric Industrial Co., Ltd. | Chemisorptive substance, aligned liquid-crystal film and liquid-crystal display element both made by using the same, and processes for producing these |
| KR100376368B1 (en) * | 1997-07-31 | 2003-03-15 | 마츠시타 덴끼 산교 가부시키가이샤 | Chemisorptive substance and processes for producing these |
| WO2004110745A1 (en) * | 2003-06-11 | 2004-12-23 | Sharp Kabushiki Kaisha | Functional organic thin film, organic thin-film transistor and methods for producing these |
| WO2005117157A1 (en) * | 2004-05-27 | 2005-12-08 | Sharp Kabushiki Kaisha | Organic compound having at both ends different functional groups differing in reactivity in elimination reaction, organic thin films, organic device, and processes for producing these |
| WO2006022176A1 (en) * | 2004-08-24 | 2006-03-02 | Sharp Kabushiki Kaisha | Organic silane compound, process for producing the compound, and organic thin film comprising the compound |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69322176D1 (en) | 1999-01-07 |
| DE69322176T2 (en) | 1999-04-22 |
| JPH08846B2 (en) | 1996-01-10 |
| EP0552637A1 (en) | 1993-07-28 |
| EP0552637B1 (en) | 1998-11-25 |
| US5270417A (en) | 1993-12-14 |
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